Switchable Nonionic to Cationic Ethoxylated Amine Surfactants for CO2 Enhanced Oil Recovery in High-Temperature, High-Salinity Carbonate Reservoirs

Abstract

Summary To improve sweep efficiency for carbon dioxide (CO2) enhanced oil recovery (EOR) up to 120°C in the presence of high-salinity brine (182 g/L NaCl), novel CO2/water (C/W) foams have been formed with surfactants composed of ethoxylated amine headgroups with cocoalkyl tails. These surfactants are switchable from the nonionic (unprotonated amine) state in dry CO2 to cationic (protonated amine) in the presence of an aqueous phase with a pH less than 6. The high hydrophilicity in the protonated cationic state was evident in the high cloudpoint temperature up to 120°C. The high cloud point facilitated the stabilization of lamellae between bubbles in CO2/water foams. In the nonionic form, the surfactant was soluble in CO2 at 120°C and 3,300 psia at a concentration of 0.2% (w/w). C/W foams were produced by injecting the surfactant into either the CO2 phase or the brine phase, which indicated good contact between phases for transport of surfactant to the interface. Solubility of the surfactant in CO2 and a favorable C/W partition coefficient are beneficial for transport of surfactant with CO2-flow pathways in the reservoir to minimize viscous fingering and gravity override. The ethoxylated cocoamine with two ethylene oxide (EO) groups was shown to stabilize C/W foams in a 30-darcy sandpack with NaCl concentrations up to 182 g/L at 120°C and 3,400 psia, and foam qualities from 50 to 95%. The foam produces an apparent viscosity of 6.2 cp in the sandpack and 6.3 cp in a 762-μm-inner-diameter capillary tube (downstream of the sandpack) in contrast with values well below 1 cp without surfactant present. Moreover, the cationic headgroup reduces the adsorption of ethoxylated alkyl amines on calcite, which is also positively charged in the presence of CO2 dissolved in brine. The surfactant partition coefficients (0 to 0.04) favored the water phase over the oil phase, which is beneficial for minimizing losses of surfactant to the oil phase for efficient surfactant usage. Furthermore, the surfactant was used to form C/W foams, without forming stable/viscous oil/water (O/W) emulsions. This selectivity is desirable for mobility control whereby CO2 will have low mobility in regions in which oil is not present and high contact with oil at the displacement front. In summary, the switchable ethoxylated alkyl amine surfactants provide both high cloudpoints in brine and high interfacial activities of ionic surfactants in water for foam generation, as well as significant solubilities in CO2 in the nonionic dry state for surfactant injection.